WO2013139121A1

WO2013139121A1 - Preparation of aluminum phosphate molecular sieve membrane supported on porous aluminum oxide carrier

Info

Publication number: WO2013139121A1
Application number: PCT/CN2012/082950
Authority: WO
Inventors: 田志坚; 李科达; 厉晓蕾; 王磊; 马怀军; 徐仁顺; 王炳春
Original assignee: 中国科学院大连化学物理研究所
Priority date: 2012-03-21
Filing date: 2012-11-19
Publication date: 2013-09-26

Abstract

Disclosed is a process for preparing an aluminum phosphate molecular sieve membrane supported on a porous aluminum oxide carrier. By this process, various microporous aluminum phosphate molecular sieve membranes are synthesized on the surface of a supporting body, with an ionic liquid as a reaction medium, and the porous aluminum oxide carrier as the supporting body, under the auxiliary effect of a structure-directing agent. The aluminum phosphate molecular sieve membranes prepared have a good gas permeation separating performance.

Description

Preparation of aluminophosphate molecular sieve membrane supported by porous alumina support

The present invention relates to an ion thermal synthesis method for a microporous aluminum phosphate molecular sieve membrane, and more particularly to an aluminum phosphate molecular sieve membrane supported by a porous alumina support and a process for the preparation thereof. Background technique

Molecular sieves are a class of inorganic microporous materials with regular pore structure. For decades, researchers and engineers have been working to study and synthesize molecular sieves with different pore characteristics as catalysts for specific chemical reactions. With the continuous advancement of science and technology, people gradually realized that if molecular sieves can be prepared into membranes, they can combine the characteristics of molecular sieve materials and thin film materials, and greatly broaden their application fields: accurate molecular screening function using molecular sieve microporous channels At the same time, combined with thin film material as a separation film, it has high efficiency, low energy consumption, continuous production, flexibility and environmental protection, and achieves efficient and continuous separation of mixed components. Today, due to the variety of skeleton pore structures of molecular sieve materials, coupled with the variability of the microstructure of membrane materials, research reports on molecular sieve membranes are increasing, and this field will continue to flourish.

The traditional synthetic methods for molecular sieve membrane preparation are as follows: (1) In-situ growth method, the substrate is directly immersed in the synthetic liquid, and the molecular sieve membrane is obtained after crystallization treatment ^ Mat^ 2006, 18, 2601-2603); (2) The secondary growth method is also the most commonly used membrane-forming strategy. A pre-synthesized nano-sized molecular sieve crystal is first attached to the substrate as a seed crystal, and then immersed in the synthetic liquid to continue crystallization to form a continuous molecular sieve membrane Mater. 2008, 20, 729-732). The above preparation methods all have certain deficiencies: The in-situ synthesis method has strict requirements on the substrate and the synthesis conditions; the secondary synthesis method inevitably prepares the nano-scale molecular sieve crystal as a seed crystal in advance, and the coating process is complicated and complicated. In addition, since both methods are based on hydrothermal synthesis technology, the system self-generated pressure generated during the synthesis process will cause certain safety hazards; in addition, a large amount of acid-base waste liquid generated during the synthesis process will also cause environmental damage. Certain pollution. The molecular sieve membrane prepared by the traditional method is mainly a silica-alumina membrane. There are few reports on the preparation of the aluminum phosphate molecular sieve membrane. So far, only AFI-type Microporous Mesoporous Mater. 2009, 126, 81-86), CHA type (J Membr. Sic) A few reports, such as 2003, 214, 191-198), LTA type (J Am. Chem. Soc. 2010, 132, 2140-2141), indicate that the conventional method has certain difficulties in the synthesis of aluminum phosphate molecular sieve membrane.

In 2004, Professor Russel E Morris of the University of St. Andrews in the United Kingdom and others reported the use of ionic liquids as solvents and templating agents to synthesize microporous aluminum phosphate molecular sieves by ionic thermal synthesis, namely ion thermal synthesis. The ionic liquid is a low-temperature molten salt having a melting point near room temperature, and is generally composed of an organic cation and an inorganic anion. Compared with the traditional molecular solvent, the ionic liquid has almost zero vapor pressure and is a non-volatile liquid; therefore, compared with the conventional hydrothermal synthesis and solvothermal synthesis, the ionic thermal synthesis reaction can be carried out under normal pressure, thus It can eliminate the safety hazard caused by the high pressure of solvent self-generated during the reaction. In addition, in the process of ionic thermal synthesis of inorganic materials, ionic liquids can be used not only as solvents, but also as templating agents in the synthesis reaction. These characteristics are in line with the requirements of green chemistry, and the synthesis process is very safe and environmentally friendly.

From the above introduction of molecular sieve membrane and ionic thermal synthesis, it can be seen that if the ion thermal method can be applied to the synthesis of molecular sieve membranes, it is expected to develop a simple, environmentally friendly and rapid method for preparing molecular sieve membranes. Summary of the invention

The object of the present invention is to provide a method for preparing an aluminum phosphate molecular sieve membrane supported by a porous alumina support. The synthesis method provided by the invention adopts the characteristics of the synthesis method: using an ionic liquid as a reaction medium, and using a porous alumina carrier as a support, a microporous aluminum phosphate molecular sieve membrane is synthesized on the surface of the support with the aid of a structure directing agent.

The specific operation process is as follows.

Preparation of precursor reaction solution: The (liquid or solid) ionic liquid is mixed with the phosphorus-containing raw material, the fluorine-containing raw material and the organic amine, and stirred to form a precursor reaction solution, and the reaction solution is P ₂ 0 ₅ : F : organic amine: The molar ratio of the ionic liquid is 1: 0~10: 0-10: 20-400;

For the ionic liquid which is liquid at normal temperature or can form a solution directly after mixing with the reactant, the precursor reaction solution does not need to be heated during preparation; for the ionic liquid which is still solid after mixing and stirring, it should be higher than its melting point. Preparation of the precursor reaction solution at a temperature (temperature can be 80~120 ° C);

The porous alumina carrier is placed in the above precursor reaction solution, and the crystallization reaction is carried out at 100 to 300 ° C, and the crystallization reaction time is ≥ 1 minute;

After the crystallization was completed, the porous alumina carrier was taken out, and the organic template was removed to obtain an aluminum phosphate molecular sieve membrane. By adjusting the composition of the structure directing agent in the above manner, the crystal structure and orientation of the obtained molecular sieve membrane can be changed:

1) When the structure directing agent is an ionic liquid cation, the molecular sieve crystal of the obtained molecular sieve membrane has an AFO structure confirmed by the International Zeolite Association, and the AFO structure aluminum phosphate molecular sieve has a one-dimensional elliptical 10-membered ring straight channel with a pore size of 0.70 nm x 0.43 nm. Its X-ray diffraction spectrum has at least the following diffraction peaks:

2Θ indicates the position of the diffraction peak, 2θ/°: 6.80±0.2; 9.77±0.2; 13.63±0.2; 18.35±0.2; 20.52±0.2; 21.27±0.2; 22.33±0.2; 22.95±0.2; 23.45±0.2; 25.40±0.2 25.81±0.2; 28.16±0.2; 29.56±0.2; 2) When the structure directing agent is an ionic liquid cation and F-, the molecular sieve crystal of the obtained molecular sieve membrane has the AEL structure confirmed by the International Zeolite Association, and the molecular sieve constituting the molecular sieve membrane The crystal has a one-dimensional ten-membered ring straight pore structure with a pore size of 0.65 nm x 0.40 nm, and its X-ray diffraction spectrum has at least the following diffraction peaks:

2Θ indicates the position of the diffraction peak, 2θ/°: 8.03±0.2; 9.40±0.2; 13.12±0.2; 15.63±0.2; 16.20±0.2; 18.95±0.2; 20.37±0.2; 20.93±0.2; 22.10±0.2; 22.43±0.2 22.70±0.2; 23.17±0.2; 24.70±0.2; 26.54±0.2;

The orientation of the AEL zeolite membrane can be adjusted by adjusting the concentration of F- in the precursor reaction solution;

3) When the structure directing agent is ionic liquid cation, F- and tetraethylammonium chloride, the molecular sieve crystal of the obtained molecular sieve membrane has the AFI structure confirmed by the International Zeolite Association, and the AFI structural aluminum phosphate molecular sieve has a one-dimensional twelve-membered ring channel. The pore size is 0.73 _n mx0.73 nm, and the X-ray diffraction spectrum thereof has at least the following diffraction peaks: 2Θ indicates the position of the diffraction peak, 2θ/°: 7.80±0.2; 13.27±0.2; 15.28±0.2; 20.15± 0.2; 21.36 ± 0.2;

22.79±0.2; 25.12±0.2; 26.36±0.2; 29.42±0.2;

4) When the structure directing agent is an ionic liquid cation, F- and Ν-methylimidazole, the molecular sieve crystal of the obtained molecular sieve membrane has a CHA structure confirmed by the International Zeolite Association, and the molecular sieve crystal structure constituting the molecular sieve membrane comprises a double six-membered ring. The connected chabazite cage has an eight-membered ring window and an adjacent four-ring structure having a pore size of 0.38 nm x 0.38 nm, and the X-ray diffraction spectrum has at least the following diffraction peaks:

2Θ indicates the position of the diffraction peak, 2θ/°: 9.40±0.2; 12.05±0.2; 13.81±0.2; 15.20±0.2; 15.53±0.2; 17.87±0.2; 18.45±0.2; 19.35±0.2; 19.75±0.2; 21.31±0.2 21.74±0.2; 22.50±0.2; 23.23±0.2; 23.85±0.2; 24.28±0.2; 25.06±0.2; 26.15±0.2;

5) When the structure directing agent is ionic liquid cation, F- and tetramethylammonium hydroxide, the molecular sieve crystal of the obtained molecular sieve membrane has the LTA structure confirmed by the International Zeolite Association, and the molecular sieve crystal structure constituting the molecular sieve membrane A three-dimensional cross-cell structure having a super-cage structure with an eight-membered ring window formed by a SOD cage through a double four-membered ring, having a pore size of 0.41 _n mx 0.41 nm, and having an X-ray diffraction spectrum having at least the diffraction peaks listed below :

2Θ indicates the position of the diffraction peak, 2θ/°: 7.28±0.2; 10.34±0.2; 12.49±0.2; 12.69±0.2; 14.72±0.2; 16.47±0.2; 18.06±0.2; 20.91±0.2; 21.88±0.2; 22.22±0.2 ; 23.44 ± 0.2; 24.61 ± 0.2; 26.81 ± 0.2; 27.84 ± 0.2.

The ionic liquid in the above synthesis method has the following cations: alkyl quaternary ammonium salt [NR4] ⁺ , alkyl quaternary phosphonium ion [PR4] ⁺ , alkyl substituted imidazolium ion [Rim] ⁺ , alkyl substituted pyridinium [ An ionic liquid of one of Rpy] ⁺ , R is a C1 to C16 alkyl group; the anion of the ionic liquid may be: Br -, Cl\ Γ, BF ₄ -, PF ₆ \ P0 ₄ ³ -, N0 ₃ -, One of S0 ₄ ² —.

The pitiful material is one of phosphoric acid, ammonium phosphate, monoammonium phosphate or ammonium dihydrogen phosphate, preferably 85% phosphoric acid. The fluorine-containing raw material is one of hydrofluoric acid, ammonium fluoride or sodium fluoride, preferably 40% hydrofluoric acid.

A porous alumina carrier is used as a support. The porous alumina carrier is prepared by extrusion, casting or bonding; the shape is a circular sheet shape, a polygonal sheet shape or a cylindrical tube shape; the material is γ-alumina, δ-alumina or Θ-alumina.

In the above synthesis method, the preferred molar ratio of Ρ ₂ 0 ₅ : F : organic amine: ionic liquid in the precursor reaction solution is 1: 0 to 2: 0-2: 20 to 160.

The preferred crystallization temperature in the above synthetic method step is 120 to 280 ° C, and the preferred crystallization time is 0.5 to crystallization. After the crystallization is completed, the synthesized molecular sieve film is subjected to X-ray diffraction characterization to determine its structure. For the molecular sieve membrane synthesized on the sheet carrier, the surface thereof can be directly characterized; for the molecular sieve membrane synthesized on the tubular carrier, the molecular sieve crystal on the surface of the carrier is scraped and characterized.

The method for removing the templating agent in the pores of the molecular sieve membrane is as follows: rising from room temperature to 500 to 550 ° C at a heating rate of 0.2 to 1 K/min under an air atmosphere, and maintaining for 4 to 8 hours; or under an inert gas (nitrogen) atmosphere Raise from room temperature to 500~550 ° C at a heating rate of 0.2~lK/min and keep it for 4~8h; or increase from room temperature to 150~250°C at a heating rate of l~5K/min under ozone atmosphere And keep 4~8h;

The permeation performance of the molecular sieve membrane from which the templating agent was removed was analyzed by a one-component gas permeation test, that is, the flow rate of different gases passing through a molecular sieve membrane per unit time was measured under a certain temperature and pressure condition, and the ratio of the flow rates of different gases was compared. And the size of the corresponding Knudsen diffusion coefficient to determine whether the measured molecular sieve membrane has better gas permeation separation performance.

The invention combines an ionic liquid and a structure directing agent to prepare an aluminum phosphate molecular sieve membrane which is difficult to prepare under hydrothermal conditions. The porous alumina carrier directly participates in the synthesis reaction as a support and an aluminum source, and overcomes the difficulty in that the molecular sieve seed crystals required for film formation are difficult to adhere to the surface of the carrier under ionic heat conditions. The ionic liquid vapor pressure is almost zero, and the present invention does not produce system autogenous high pressure during the preparation process. The synthesized zeolite membrane has good gas separation and permeation properties. The method of the invention has the advantages of environmental friendliness and simple operation, and is particularly advantageous for large-scale production of molecular sieve membranes. DRAWINGS

1 is an XRD spectrum of an AFO-type aluminum phosphate molecular sieve membrane synthesized in Example 1 of the present invention; FIG. 2 is a SEM electron micrograph of an AFO-type aluminum phosphate molecular sieve membrane synthesized in Example 1 of the present invention; One-component gas permeation experiment of AFO type aluminum phosphate molecular sieve membrane synthesized in Example 1 Data

4 is an XRD spectrum of an AEL type aluminum phosphate molecular sieve film synthesized in Example 1 of the present invention; FIG. 5 is a SEM electron micrograph of an AEL type aluminum phosphate molecular sieve film synthesized in Example 1 of the present invention; One-component gas permeation experimental data of the AEL type aluminum phosphate molecular sieve membrane synthesized in Example 1;

Figure 7 is an XRD chart of a highly C-axis oriented AEL type aluminum phosphate molecular sieve film synthesized in Example 1 of the present invention;

Figure 8 is a SEM electron micrograph of a highly C-axis oriented AEL type aluminum phosphate molecular sieve film synthesized in Example 1 of the present invention;

Figure 9 is a single component gas permeation experimental data of a highly C-axis oriented AEL type aluminum phosphate molecular sieve membrane synthesized in Example 1 of the present invention;

10 is an XRD spectrum of an AFI-type aluminum phosphate molecular sieve membrane synthesized in Example 1 of the present invention; FIG. 11 is a SEM electron micrograph of an AFI-type aluminum phosphate molecular sieve membrane synthesized in Example 1 of the present invention; One-component gas permeation experimental data of the AFI-type aluminum phosphate molecular sieve membrane synthesized in Example 1;

13 is an XRD spectrum of a CHA-type aluminum phosphate molecular sieve membrane synthesized in Example 1 of the present invention; FIG. 14 is a SEM electron micrograph of a CHA-type aluminum phosphate molecular sieve membrane synthesized in Example 1 of the present invention; FIG. One-component gas permeation experimental data of the CHA type aluminum phosphate molecular sieve membrane synthesized in Example 1;

16 is an XRD spectrum of an LTA type aluminum phosphate molecular sieve film synthesized in Example 1 of the present invention; FIG. 17 is a SEM electron micrograph of an LTA type aluminum phosphate molecular sieve film synthesized in Example 1 of the present invention; One-component gas permeation experimental data of the LTA type aluminum phosphate molecular sieve membrane synthesized in Example 1.

Figure 19 is a schematic diagram of a single component gas permeation experimental apparatus for the synthesized aluminum phosphate molecular sieve membrane according to the present invention, wherein 1-stop valve; 2-pressure reducing valve; 3-precision pressure gauge; 4-stop valve; 5-needle Valve; 6-soap membrane flowmeter; 7-permeation device; 8-molecular sieve membrane. detailed description

When synthesizing AFO type zeolite membrane, the specific operation process is as follows:

1) preparing a precursor reaction solution: mixing the ionic liquid with the phosphorus-containing raw material, stirring to form a precursor reaction solution, the molar ratio of P ₂ 0 ₅ : ionic liquid in the reaction solution is 1: 10-400;

2) The porous alumina carrier is placed in the above precursor reaction solution, and the crystallization reaction is carried out at 100 to 300 ° C, and the crystallization reaction time is ≥ 1 minute;

3) After the crystallization is completed, the porous alumina carrier is taken out, and the organic template is removed to obtain an AFO aluminum phosphate molecular sieve membrane. The molar ratio of P ₂ O ₅ : ionic liquid in the precursor reaction solution is preferably 1:20 to 200.

When synthesizing AEL type zeolite membrane, the specific operation process is as follows:

1) Preparation of precursor reaction solution: Mixing ionic liquid with phosphorus-containing raw material, mineralizer and organic amine, and stirring to form precursor reaction solution, P ₂ 0 ₅ in the reaction solution: mineralizer: molar ratio of ionic liquid For 1: 0.1~2: 40~ shed;

2) placing a porous alumina carrier into the above precursor reaction solution, and performing crystallization reaction at 100 to 300 ° C, Crystallization reaction time ≥ 1 minute;

3) After the crystallization is completed, the porous alumina carrier is taken out, and the organic template is removed to obtain an AEL aluminum phosphate molecular sieve membrane.

The mineralizer added is a compound containing F, and the molar ratio of F to the ionic liquid in the precursor reaction solution is preferably 1:400 to 1600.

The molar ratio of P ₂ 0 ₅ : F- : ionic liquid in the precursor reaction is preferably 1: 0.2 〜1: 80-320 When synthesizing a highly C-axis oriented AEL type molecular sieve, the specific operation is as follows:

1) Preparation of precursor reaction solution: Add phosphorus-containing raw material, fluorine-containing raw material and N-methylimidazole to the ionic liquid, and stir to form a precursor reaction solution. P ₂ 0 ₅ : F : molar solution of ionic liquid in the reaction solution The ratio is 1: 1~20: 40~ shed;

2) For the ionic liquid which is liquid at normal temperature or can form a solution directly after mixing with the reactant, the precursor reaction solution does not need to be heated during preparation; for the ionic liquid which is still solid after mixing and stirring, it should be higher than Preparing a precursor reaction solution at a temperature of a melting point (temperature may be 80 to 120 ° C);

3) The porous alumina carrier is placed in the above precursor reaction solution, and the crystallization reaction is carried out at 100 to 300 ° C, and the crystallization reaction time is ≥ 1 minute;

After the crystallization was completed, the porous alumina carrier was taken out, and the organic template was removed to obtain a highly C-axis oriented AEL aluminum phosphate molecular sieve membrane.

The mineralizer added is a compound containing F, and the molar ratio of F to the ionic liquid in the precursor reaction solution is preferably 1:20 to 160.

The molar ratio of P ₂ 0 ₅ : mineralizer F: ionic liquid in the precursor reaction solution is preferably 1: 1 to 4:

40~160.

When synthesizing AFI type zeolite membrane, the specific operation process is as follows:

1) Preparation of the precursor reaction solution: The (liquid or solid) ionic liquid and the phosphorus-containing raw material, the fluorine-containing raw material and the tetraethylammonium chloride are uniformly stirred to form a precursor reaction solution, and the reaction solution is P ₂ 0 ₅ : F-: tetraethylammonium chloride: the molar ratio of ionic liquid is 1: 0.1~10: 0.1-10: 20-400;

3) After the crystallization is completed, the porous alumina carrier is taken out, and the organic template is removed to obtain an AFI aluminum phosphate molecular sieve membrane.

The organic amine template added is tetraethylammonium chloride, which is combined with the phosphorus-containing compound in the precursor reaction solution.

The molar ratio of P ₂ 0 ₅ is preferably 1:0.2 to 5.

The molar ratio of P ₂ 0 ₅ : F" : organic amine: ionic liquid in the precursor reaction solution is preferably 1: 0.2 to 2: 0.2-2: 40 to 160.

When synthesizing CHA type zeolite membrane, the specific operation process is as follows:

1) Preparation of precursor reaction solution: Mixing the ionic liquid with the phosphorus-containing raw material, the fluorine-containing raw material and the organic amine, and uniformly stirring to form a precursor reaction solution, and the reaction solution is P ₂ 0 ₅ : F : organic amine: molar of the ionic liquid The ratio is 1: 0.1~10: 0.1-10: 20-400;

3) After the crystallization is completed, the porous alumina carrier is taken out, and the organic template is removed to obtain a CHA aluminum phosphate molecular sieve. Membrane.

The organic amine templating agent added is N-methylimidazole, and the phosphorus-containing compound is calculated as P ₂ 0 ₅ , and the molar ratio thereof to the phosphorus-containing compound in the precursor reaction solution is preferably 1:0.2 to 5.

When synthesizing LTA type zeolite membrane, the specific operation process is as follows:

1) Preparation of precursor reaction solution: adding phosphorus-containing raw material, fluorine-containing raw material and organic amine to the ionic liquid, and stirring to form a precursor reaction solution, P ₂ 0 ₅ : F in the reaction solution: organic amine: molar of ionic liquid The ratio is 1: 0.1~10: 0.1-10: 10-300;

3) After the crystallization is completed, the porous alumina carrier is taken out, and the organic template is removed to obtain an LTA-type aluminum phosphate molecular sieve membrane.

The organic amine template added is a tetramethylammonium hydroxide aqueous solution having a mass concentration of 25%, and the phosphorus-containing compound is calculated as P ₂ 0 ₅ , and the molar ratio of the phosphorus-containing compound to the phosphorus-containing compound in the precursor reaction solution is preferably 1:0.2. ~5.

The molar ratio of P ₂ 0 ₅ : F" : organic amine: ionic liquid in the precursor reaction solution is preferably 1: 0.2 to 2: 0.2-2: 20 to 150.

Example 1

57.3 g of 1-ethyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 100 ° C, and 1.15 g of 85% by mass of phosphoric acid, P ₂ O ₅ : ionic liquid was added dropwise thereto. The molar ratio is 1:60, stirred for 2 hours until homogeneous, and then the reaction liquid is poured into a reactor in which a δ-round flaky alumina carrier is placed in advance, and the carrier is completely immersed in the reaction liquid, and the support and the support are The amount of the precursor reaction solution was O. cm^mr ¹ support surface area), the reactor was heated to 140 ° C for 48 hours, then the reactor was cooled to room temperature, the carrier was taken out, and ultrasonically washed three times in deionized water. And wash it with acetone. The washed carrier was dried in an oven at 110 °C. The organic substance in the pores of the molecular sieve membrane was removed by raising the temperature to a temperature of 1 K/min to 550 ° C in an air atmosphere for 6 hours to obtain an AFO type molecular sieve membrane.

It can be seen from Fig. 1 that the prepared molecular sieve membrane is pure phase and free of heterocrystals; as can be seen from Fig. 2, the prepared molecular sieve membrane is dense, complete and continuous; the thickness is about 20 micrometers; The prepared molecular sieve membrane has good gas permeability.

Example 2

57.3 g of 1-ethyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 100 ° C, and 2.30 g of a 85% by mass phosphoric acid, P ₂ O ₅ : ionic liquid was added dropwise thereto. The molar ratio is 1:30, stirred for 2 hours to homogeneity, and then the reaction liquid is poured into a reactor in which a δ-circular flaky alumina carrier is placed in advance, and the carrier is completely immersed in the reaction liquid, and the support is The ratio of the precursor reaction solution was (^(cn^mr ¹ support surface area), the reactor was heated to 160 ° C for 24 hours, then the reactor was cooled to room temperature, the carrier was taken out, and ultrasonically washed in deionized water. Three times, and washed with acetone soaked. The washed carrier was dried in an oven at 110 ° C. It was raised to 550 ° C at a heating rate of 1 K / min in an air atmosphere for 6 h to remove organic matter in the pores of the molecular sieve membrane. Thereby, an AFO type molecular sieve membrane is obtained.

Example 3

57.3 g of 1-ethyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker and the temperature was raised to 90 ° C. 3.45 g of phosphoric acid having a mass concentration of 85% was added dropwise thereto, and the molar ratio of P ₂ O ₅ : ionic liquid was 1:20, stirred for 2 hours until homogeneous, and then the reaction solution was poured into a pre-placed Θ-round sheet. In the alumina carrier reactor, it is noted that the carrier needs to be completely immersed in the reaction solution, and the ratio of the support to the precursor reaction solution is (^(cn^mr ¹ support surface area), and the reactor is heated to 160 ° C, After maintaining for 24 hours, the reactor was then cooled to room temperature, the carrier was taken out, ultrasonically washed three times in deionized water, and washed with acetone. The washed carrier was dried in an oven at 110 ° C. In an air atmosphere at 1 K / The heating rate of min was raised to 550 ° C for 6 h, and the organic matter in the pores of the molecular sieve membrane was removed to obtain an AFO type molecular sieve membrane.

Example 4

57.3 g of 1-ethyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 120 ° C, and 0.35 g of a 85% by mass phosphoric acid, P ₂ O ₅ : ionic liquid was added dropwise thereto. The molar ratio is 1:200, stirred for 2 hours to homogeneity, and then the reaction liquid is poured into a reactor in which a ruthenium-cylindrical tubular alumina carrier is placed in advance, and the carrier needs to be completely immersed in the reaction liquid, the support body and the front The amount of the body reaction solution is O cm ^ mr ¹ support surface area), the reactor is heated to 140 ° C for 240 hours, then the reactor is cooled to room temperature, the carrier is taken out, ultrasonically washed three times in deionized water, and used Acetone soaked and washed. The washed carrier was dried in an oven at 110 °C. The organic matter in the pores of the molecular sieve membrane was removed by a temperature increase of 1 K/min in a nitrogen atmosphere at 550 ° C for 6 hours to obtain an AFO-type molecular sieve membrane.

Example 5

65.7 g of 1-butyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 100 ° C, and 0.58 g of a 85% by mass phosphoric acid, P ₂ O ₅ : ionic liquid was added dropwise thereto. The molar ratio is 1:120, stirred for 2 hours to homogeneity, and then the reaction solution is poured into a reactor in which a δ-round flaky alumina carrier is placed in advance, and the carrier is completely immersed in the reaction solution, and the support and the support are The ratio of the precursor reaction solution was (^(cn^mr ¹ support surface area). The reactor was heated to 180 ° C for 12 hours, then the reactor was cooled to room temperature, the carrier was taken out, and ultrasonically washed three times in deionized water. And washing with acetone soaked. The washed carrier was dried in an oven at 110 ° C. It was raised to 550 ° C at a heating rate of 1 K / min in a nitrogen atmosphere for 6 h to remove organic matter in the pores of the molecular sieve membrane. Thus, an AFO type molecular sieve membrane was obtained.

Example 6

57.3 g of 1-ethyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 90 ° C, and 0.70 g of a 85% by mass phosphoric acid, P ₂ O ₅ : ionic liquid was added dropwise thereto. The molar ratio is 1:100, stirred for 2 hours to homogeneity, and then the reaction solution is poured into a reactor in which a δ-square flaky alumina carrier is placed in advance, and the carrier is completely immersed in the reaction solution, and the support is before The amount of the body reaction solution was (^(cn^mr ¹ support surface area). The reactor was heated to 280 ° C for 0.5 hours, then the reactor was cooled to room temperature, the carrier was taken out, and ultrasonically washed three times in deionized water. And washing with acetone soaked. The washed carrier was dried in an oven at 110 ° C. It was raised to 140 ° C at a heating rate of 4 K / min in an air atmosphere containing 50 mg / L of ozone, and kept for 8 h to remove the molecular sieve membrane. The organic matter in the pores, thereby obtaining an AFO-type molecular sieve membrane.

Table 1 XRD diffraction peak positions and relative strengths of samples in Examples 1 to 6 of the present invention

It can be seen from the above table that in the range of reaction conditions stated in the method, when the structure directing agent is an ionic liquid cation, a pure phase AFO type aluminum phosphate molecular sieve membrane can be prepared.

Example 7

76.4 g of 1-ethyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 100 ° C. 0.5 g of hydrofluoric acid having a concentration of 40% was uniformly added dropwise, and stirred for 2 hours until homogeneous. 1.15 g of phosphoric acid having a mass concentration of 85% was added dropwise thereto, and the molar ratio of P ₂ 0 ₅ : F" : ionic liquid was 1:2:80, stirring was continued for 10 minutes, and then the reaction solution was poured into a pre-placed δ- In the reactor with a circular flake alumina support, note that the support should be completely immersed in the reaction solution. The ratio of the support to the precursor reaction solution is 0.5 (cn^mr ¹ support surface area), and the reactor is heated to 150. °C, held for 12 hours, then the reactor was cooled to room temperature, the carrier was taken out, ultrasonically washed three times in deionized water, and washed with acetone. The washed carrier was dried in an oven at 110 ° C. In an air atmosphere The organic matter in the pores of the molecular sieve membrane was removed by raising the temperature from room temperature to 550 ° C at a heating rate of 1 K/min for 6 hours to obtain an AEL type molecular sieve membrane.

It can be seen from Fig. 4 that the prepared molecular sieve membrane is pure phase and free of heterocrystals; as can be seen from Fig. 5, the prepared molecular sieve membrane is dense, complete and continuous; the thickness is about 15 micrometers; The prepared molecular sieve membrane has good gas permeability.

Example 8

76.4 g of 1-ethyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 120 ° C. 0.25 g of hydrofluoric acid having a concentration of 40% was uniformly added dropwise, and stirred for 2 hours until homogeneous. 0.575 g of phosphoric acid having a mass concentration of 85% was added dropwise thereto, and the molar ratio of P ₂ 0 ₅ : F : ionic liquid was 1:2:160, stirring was continued for 10 minutes, and then the reaction liquid was poured into a δ-circle previously placed. In the reactor with the flake-shaped alumina carrier, note that the carrier needs to be completely immersed in the reaction solution, and the ratio of the support to the precursor reaction solution is 0.6 (cn^mr ¹ support surface area), and the reactor is heated to 160°. C, held for 24 hours, then the reactor was cooled to room temperature, the carrier was removed, ultrasonically washed three times in deionized water, and washed with acetone. The washed carrier was placed at 110 ° C Dry in an oven. The organic matter in the pores of the molecular sieve membrane was removed by raising the temperature to a temperature of 1 K/min to 550 ° C in an air atmosphere for 6 hours to obtain an AEL type molecular sieve membrane.

Example 9

76.4 g of 1-ethyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 90 ° C. 0.1 g of hydrofluoric acid having a concentration of 40% was uniformly added dropwise, and stirred for 2 hours until homogeneous. 0.23 g of a phosphoric acid having a mass concentration of 85% was added dropwise thereto, and the molar ratio of P ₂ 0 ₅ : F" : ionic liquid was 1:2:400, stirring was continued for 10 minutes, and then the reaction liquid was poured into a pre-placed crucible - In the reactor of the square flaky alumina carrier, note that the carrier needs to be completely immersed in the reaction solution, and the ratio of the support to the precursor reaction solution is 0.4 (cn^mr ¹ support surface area), and the reactor is heated to 120°. C, held for 480 hours, then the reactor was cooled to room temperature, the carrier was taken out, ultrasonically washed three times in deionized water, and washed with acetone. The washed carrier was dried in an oven at 110 ° C. The heating rate of lK/min was raised to 550 ° C for 6 h, and the organic matter in the pores of the molecular sieve membrane was removed to obtain an AEL type molecular sieve membrane.

Example 10

76.4 g of 1-ethyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 100 ° C, and 0.05 g of a 40% by mass hydrofluoric acid was uniformly added thereto, and the mixture was stirred for 2 hours until homogeneous. To this was added dropwise 2.3 g of a phosphoric acid having a mass concentration of 85%, and the molar ratio of P ₂ 0 ₅ : F" : ionic liquid was 1: 0.1:40, stirring was continued for 10 minutes, and then the reaction solution was poured into γ-pre-placed. In the reactor of cylindrical tubular alumina carrier, note that the carrier needs to be completely immersed in the reaction solution, the ratio of the support to the precursor reaction solution is 0.5 (cn^mr ¹ support surface area), and the reactor is heated to 280 ° C, held for 0.5 hours, then the reactor was cooled to room temperature, the carrier was taken out, ultrasonically washed three times in deionized water, and washed with acetone. The washed carrier was dried in an oven at 110 ° C. The heating rate of lK/min was raised to 550 ° C for 6 h, and the organic matter in the pores of the molecular sieve membrane was removed to obtain an AEL type molecular sieve membrane.

Example 11

76.4 g of 1-ethyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 100 ° C. 0.25 g of hydrofluoric acid having a concentration of 40% was uniformly added dropwise, and stirred for 2 hours until homogeneous. 0.66 g of monoammonium phosphate was added thereto, and the molar ratio of P ₂ 0 ₅ : F : ionic liquid was 1:2:160, stirring was continued for 10 minutes, and then the reaction liquid was poured into a δ-square plate alumina which was previously placed. In the reactor of the carrier, note that the carrier needs to be completely immersed in the reaction solution, and the ratio of the support to the precursor reaction solution is 0.2 (cn^mr ¹ support surface area), and the reactor is heated to 150 ° C for 12 hours. Subsequently, the reactor was lowered to room temperature, the carrier was taken out, ultrasonically washed three times in deionized water, and washed with acetone. The washed carrier was dried in an oven at 110 °C. The organic matter in the pores of the molecular sieve membrane was removed by a temperature increase of 1 K/min to 550 ° C in a nitrogen atmosphere for 6 hours to obtain an AEL type molecular sieve membrane.

Example 12

76.4 g of 1-ethyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 90 ° C. 0.21 g of sodium fluoride was uniformly added, stirred for 2 hours until homogeneous, and 0.575 g of phosphoric acid was added thereto. Ammonium hydroxide, P ₂ 0 ₅ : F" : The molar ratio of ionic liquid is 1: 2: 160, stirring is continued for 10 minutes, and then the reaction liquid is poured into a reactor in which a δ-square flaky alumina carrier is placed in advance. Note that the carrier needs to be completely immersed in the reaction solution. The ratio of the support to the precursor reaction solution is 0.8 (cn^mr ¹ support surface area), the reactor is heated to 150 ° C for 12 hours, and then the reactor is lowered. At room temperature, the carrier was taken out, ultrasonically washed three times in deionized water, and washed with acetone. The washed carrier was dried in an oven at 110 ° C. 1 K/min in a nitrogen atmosphere. The heating rate was raised to 550 ° C for 6 h, and the organic matter in the pores of the molecular sieve membrane was removed to obtain an AEL type molecular sieve membrane.

Example 13

76.4 g of 1-ethyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, the temperature was raised to 100 ° C, 0.185 g of ammonium fluoride was uniformly added, and the mixture was stirred for 2 hours until homogeneous, and 0.575 g of the mass was added thereto. The concentration of 85% phosphoric acid, P ₂ 0 ₅ : F : ionic liquid molar ratio is 1: 2: 160, stirring is continued for 10 minutes, and then the reaction solution is poured into a reaction in which δ-round flake alumina is preliminarily placed. In the device, note that the carrier needs to be completely immersed in the reaction solution. The ratio of the support to the precursor reaction solution is 0.5 (cn^mr ¹ support surface area), and the reactor is heated to 150 ° C for 12 hours, then The reactor was cooled to room temperature, the carrier was removed, ultrasonically washed three times in deionized water, and washed with acetone. The washed carrier was dried in an oven at 110 °C. In an air atmosphere containing 50 mg/L of ozone, the temperature was raised to 140 ° C at a heating rate of 4 K/min, and held for 8 hours, and the organic matter in the pores of the molecular sieve membrane was removed to obtain an AEL type molecular sieve membrane.

Example 14

82.0 g of 1-propyl-3-methylimidazolium chloride ionic liquid was added to a 100 ml beaker, and the temperature was raised to 90 ° C. 0.0925 g of ammonium fluoride and 0.105 g of sodium fluoride were uniformly added, and stirred for 2 hours until homogeneous. 0.33 g of ammonium monohydrogen phosphate and 0.29 g of ammonium dihydrogen phosphate were added, and the molar ratio of P ₂ 0 ₅ : F" : ionic liquid was 1:2:160, stirring was continued for 10 minutes, and then the reaction liquid was poured into the pre-placement. In the reactor of δ-cylindrical tubular alumina, note that the carrier needs to be completely immersed in the reaction solution. The ratio of the support to the precursor reaction solution is 0.5 (cm^mr ¹ support surface area), and the reactor is heated to 150. °C, hold for 12 hours, then the reactor was cooled to room temperature, the carrier was taken out, ultrasonically washed three times in deionized water, and washed with acetone. The washed carrier was dried in an oven at 110 ° C. 50 mg in ozone. The air atmosphere of /L was raised to 200 ° C at a heating rate of 4 K / min, and held for 6 h, and the organic matter in the pores of the molecular sieve membrane was removed to obtain an AEL type molecular sieve membrane.

Table 2 XRD diffraction peak positions and relative strengths of the samples in Examples 7 to 14 of the present invention

26.54±0.2 Weakness, Weakness, Weakness, Weakness and Weakness As can be seen from the above table, pure phase AEL type aluminum phosphate zeolite membrane can be prepared by using ionic liquid cation and F- as structure directing agent within the reaction conditions stated in the method. .

Example 15

76.4 g of 1-ethyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 100 ° C. 0.5 g of hydrofluoric acid having a concentration of 40% was uniformly added dropwise, and stirred for 2 hours until homogeneous. 2.3 g of phosphoric acid having a mass concentration of 85% was added dropwise thereto, and the molar ratio of P ₂ 0 ₅ : F : ionic liquid was 1: 1: 40, stirring was continued for 10 minutes, and then the reaction liquid was poured into a δ-circle previously placed. In the reactor with the flake-shaped alumina carrier, note that the carrier needs to be completely immersed in the reaction solution, and the ratio of the support to the precursor reaction solution is 0.5 (cn^mr ¹ support surface area), and the reactor is heated to 150°. C, held for 12 hours, then the reactor was cooled to room temperature, the carrier was removed, ultrasonically washed three times in deionized water, and washed with acetone. The washed carrier was dried in an oven at 110 °C. The organic matter in the pores of the molecular sieve membrane was removed in the air atmosphere at a temperature increase rate of 1 K/min from room temperature to 550 ° C for 6 hours to obtain a highly oriented AEL type molecular sieve membrane.

It can be seen from Fig. 7 that the prepared molecular sieve membrane is pure phase and contains no crystal; as can be seen from Fig. 8, the prepared molecular sieve membrane is dense, complete and continuous; the thickness is about 40 microns; The prepared molecular sieve membrane has good gas permeability.

Example 16

76.4 g of 1-ethyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 120 ° C. 1 g of hydrofluoric acid having a concentration of 40% was uniformly added dropwise, and stirred for 2 hours until homogeneous. 1.15 g of phosphoric acid having a mass concentration of 85% was added dropwise thereto, and the molar ratio of P ₂ 0 ₅ : F : ionic liquid was 1:4:80, stirring was continued for 10 minutes, and then the reaction solution was poured into a pre-placed δ-circle. In the reactor with the flake-shaped alumina carrier, note that the carrier needs to be completely immersed in the reaction solution, and the ratio of the support to the precursor reaction solution is 0.6 (cn^mr ¹ support surface area), and the reactor is heated to 160°. C, held for 24 hours, then the reactor was cooled to room temperature, the carrier was removed, ultrasonically washed three times in deionized water, and washed with acetone. The washed carrier was dried in an oven at 110 °C. The organic matter in the pores of the molecular sieve membrane was removed in an air atmosphere at a heating rate of 1 K/min to 550 ° C for 6 hours to obtain a highly oriented AEL type molecular sieve membrane.

Example 17

76.4 g of 1-ethyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 90 ° C. 1 g of hydrofluoric acid having a concentration of 40% was uniformly added dropwise, and stirred for 2 hours until homogeneous. 0.23 g of phosphoric acid having a mass concentration of 85% was added dropwise thereto, and the molar ratio of P ₂ 0 ₅ : F : ionic liquid was 1:20:200, stirring was continued for 10 minutes, and then the reaction solution was poured into a pre-placed Θ-square. In the reactor of the flaky alumina carrier, note that the carrier needs to be completely immersed in the reaction solution, and the ratio of the support to the precursor reaction solution is 0.4 (cn^mr ¹ support surface area), and the reactor is heated to 120 ° C. After maintaining for 480 hours, the reactor was then cooled to room temperature, the carrier was taken out, ultrasonically washed three times in deionized water, and washed with acetone. The washed carrier was dried in an oven at 110 °C. The organic matter in the pores of the molecular sieve membrane was removed in an air atmosphere at a heating rate of 1 K/min to 550 ° C for 6 hours to obtain a highly oriented AEL type molecular sieve membrane.

Example 18

76.4 g of 1-ethyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 100 ° C. 2 g of hydrofluoric acid having a mass concentration of 40% was uniformly added dropwise, and stirred for 2 hours until homogeneous. 1.15 g of phosphoric acid having a mass concentration of 85% was added dropwise thereto, and the molar ratio of P ₂ 0 ₅ : F : ionic liquid was 1:8:80, and stirring was continued. After 10 minutes, the reaction solution was poured into a reactor in which a γ-cylindrical tubular alumina carrier was placed in advance, and the carrier was completely immersed in the reaction solution, and the ratio of the support to the precursor reaction solution was 0.5 (cn^ The mr ¹ support surface area), the reactor was heated to 280 ° C for 0.5 hours, then the reactor was cooled to room temperature, the carrier was taken out, ultrasonically washed three times in deionized water, and washed with acetone. The washed carrier was dried in an oven at 110 °C. The organic matter in the pores of the molecular sieve membrane was removed in an air atmosphere at a heating rate of 1 K/min to 550 ° C for 6 hours to obtain a highly oriented AEL type molecular sieve membrane.

Example 19

76.4 g of 1-ethyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 100 ° C. 1 g of hydrofluoric acid having a concentration of 40% was uniformly added dropwise, and stirred for 2 hours until homogeneous. To this was added 1.32 g of monoammonium phosphate, P ₂ 0 ₅ : F" : the molar ratio of ionic liquid was 1: 4: 80, stirring was continued for 10 minutes, and then the reaction solution was poured into a pre-placed δ-square sheet oxidation. In the aluminum carrier reactor, note that the carrier needs to be completely immersed in the reaction solution. The ratio of the support to the precursor reaction solution is 0.2 (cn^mr ¹ support surface area), and the reactor is heated to 150 ° C to maintain 12 After the hour, the reactor was then cooled to room temperature, the carrier was taken out, ultrasonically washed three times in deionized water, and washed with acetone. The washed carrier was dried in an oven at 110 ° C. In a nitrogen atmosphere at 1 K/min. The heating rate was raised to 550 ° C for 6 h, and the organic matter in the pores of the molecular sieve membrane was removed to obtain a highly oriented AEL type molecular sieve membrane.

Example 20

76.4 g of 1-ethyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, the temperature was raised to 90 ° C, 0.84 g of sodium fluoride was uniformly added, and the mixture was stirred for 2 hours until homogeneous, and 1.15 g of phosphoric acid was added thereto. Ammonium hydroxide, P ₂ 0 ₅ : F" : The molar ratio of ionic liquid is 1: 4: 80, stirring is continued for 10 minutes, and then the reaction liquid is poured into a reactor in which a δ-square flaky alumina carrier is placed in advance. Note that the carrier needs to be completely immersed in the reaction solution. The ratio of the support to the precursor reaction solution is 0.8 (cn^mr ¹ support surface area), the reactor is heated to 150 ° C for 12 hours, and then the reactor is lowered. At room temperature, the carrier was taken out, ultrasonically washed three times in deionized water, and washed with acetone. The washed carrier was dried in an oven at 110 ° C. The temperature was raised to 550 ° C at a heating rate of 1 K / min in a nitrogen atmosphere. And for 6 h, the organic matter in the pores of the molecular sieve membrane was removed, thereby obtaining a highly oriented AEL type molecular sieve membrane.

Example 21

76.4 g of 1-ethyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, the temperature was raised to 100 ° C, 0.74 g of ammonium fluoride was uniformly added, and the mixture was stirred for 2 hours until homogeneous, and 1.15 g of mass was added thereto. Phosphoric acid with a concentration of 85%, P ₂ 0 ₅ : F : The molar ratio of ionic liquid is 1: 4: 80, stirring is continued for 10 minutes, and then the reaction solution is poured into a reaction in which δ-round flake alumina is preliminarily placed. In the device, note that the carrier needs to be completely immersed in the reaction solution. The ratio of the support to the precursor reaction solution is 0.5 (cn^mr ¹ support surface area), and the reactor is heated to 150 ° C for 12 hours, then The reactor was cooled to room temperature, the carrier was removed, ultrasonically washed three times in deionized water, and washed with acetone. The washed carrier was dried in an oven at 110 °C. The organic matter in the pores of the molecular sieve membrane was removed in an air atmosphere containing 50 mg/L of ozone at a heating rate of 4 K/min and maintained for 8 hours to obtain a highly oriented AEL type molecular sieve membrane.

Example 22

82.0 g of 1-propyl-3-methylimidazolium imide liquid was added to a 100 ml beaker, and the temperature was raised to 90 ° C. 0.37 g of ammonium fluoride and 0.42 g of sodium fluoride were uniformly added, and stirred for 2 hours until homogeneous. 0.66 g of monoammonium phosphate and 0.575 g of ammonium dihydrogen phosphate were added, and the molar ratio of P ₂ 0 ₅ : F : ionic liquid was 1:4:80. Stirring was continued for 10 minutes, and then the reaction liquid was poured into a reactor in which δ-cylindrical tubular alumina was placed in advance, and it was noted that the carrier was completely immersed in the reaction liquid, and the ratio of the support to the precursor reaction solution was 0.5 (cm). ^mr ¹ support surface area), the reactor was warmed to 150 ° C for 12 hours, then the reactor was cooled to room temperature, the support was removed, ultrasonically washed three times in deionized water, and washed with acetone. The washed carrier was dried in an oven at 110 °C. The organic matter in the pores of the molecular sieve membrane was removed in an air atmosphere containing 50 mg/L of ozone at an increase rate of 4 K/min to 200 ° C for 6 hours to obtain a highly oriented AEL type molecular sieve membrane.

Table 3 XRD diffraction peak positions and relative strengths of samples in Examples 15 to 22 of the present invention

It can be seen from the above table that, within the range of reaction conditions stated in the method, a highly oriented AEL type aluminum phosphate molecular sieve membrane can be prepared by increasing the concentration of F in the reaction solution by using ionic liquid cations and F- as a structure directing agent. .

Example 23

65.7 g of 1-butyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 100 ° C. 0.05 g of hydrofluoric acid having a concentration of 40% was uniformly added dropwise, and stirred for 2 hours until homogeneous. 0.575 g of 85% by mass phosphoric acid was added dropwise thereto, and then 0.0825 g of tetraethylammonium chloride was uniformly added, and P ₂ 0 ₅ : F : organic amine: the molar ratio of the ionic liquid was 1:0.4:0.2:120, Stirring was continued for 10 minutes, and then the reaction liquid was poured into a reactor in which a δ-round flaky alumina carrier was placed in advance, and it was noted that the carrier was completely immersed in the reaction liquid, and the ratio of the support to the precursor reaction solution was 0.5. (cn^mr ¹ support surface area), the reactor was heated to 150 ° C for 36 hours, then the reactor was cooled to room temperature, the carrier was taken out, ultrasonically washed three times in deionized water, and washed with acetone. The washed carrier was dried in an oven at 110 °C. The organic matter in the pores of the molecular sieve membrane was removed in an air atmosphere at a temperature increase rate of 1 K/min to 550 ° C for 6 hours to obtain an AFI type molecular sieve membrane.

It can be seen from Fig. 10 that the prepared molecular sieve membrane is pure phase and contains no crystals; as can be seen from Fig. 11, The prepared molecular sieve membrane is dense, complete and continuous; the thickness is about 30 microns; as can be seen from Figure 12, the prepared zeolite membrane has good gas permeability.

Example 24

65.7 g of 1-butyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 90 ° C. 0.3 g of hydrofluoric acid having a concentration of 40% was uniformly added dropwise, and stirred for 2 hours until homogeneous. 3.45 g of phosphoric acid having a mass concentration of 85% was added dropwise thereto, and then 0.495 g of tetraethylammonium chloride was uniformly added. P ₂ 0 ₅ : F : organic amine: the molar ratio of the ionic liquid was 1:0.4:0.2:20. Stirring was continued for 10 minutes, and then the reaction solution was poured into a reactor in which a γ-square platelet alumina carrier was placed in advance. Note that the carrier was completely immersed in the reaction solution, and the ratio of the support to the precursor reaction solution was Ο.支撑^η^ηιΓ ¹ support surface area), the reactor was heated to 120 ° C for 480 hours, then the reactor was cooled to room temperature, the carrier was taken out, ultrasonically washed three times in deionized water, and washed with acetone. The washed carrier was dried in an oven at 110 °C. The organic matter in the pores of the molecular sieve membrane was removed in an air atmosphere at a temperature increase rate of IK/min to 550 ° C for 6 hours to obtain an AFI type molecular sieve membrane.

Example 25

110 g of 1-butyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 100 ° C. 0.625 g of hydrofluoric acid having a concentration of 40% was uniformly added dropwise, and stirred for 2 hours until homogeneous. 0.2875 g of 85% by mass of phosphoric acid was added dropwise, and then 2.625 g of tetraethylammonium chloride was uniformly added, and P ₂ 0 ₅ : F : organic amine: the molar ratio of the ionic liquid was 1:10:10:400, Stirring was continued for 10 minutes, and then the reaction solution was poured into a reactor in which a cerium-square flaky alumina carrier was placed in advance. Note that the carrier was completely immersed in the reaction solution, and the ratio of the support to the precursor reaction solution was O. Cn^mr ¹ support surface area), the reactor was heated to 280 ° C for 0.5 hours, then the reactor was cooled to room temperature, the carrier was taken out, ultrasonically washed three times in deionized water, and washed with acetone. The washed carrier was dried in an oven at 110 °C. The organic matter in the pores of the molecular sieve membrane was removed in an air atmosphere at a temperature increase rate of IK/min to 550 ° C for 6 hours to obtain an AFI type molecular sieve membrane.

Example 26

65.7 g of 1-butyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 110 ° C, and 0.05 g of a 40% by mass hydrofluoric acid was uniformly added thereto, and the mixture was stirred for 2 hours until homogeneous. 0.575 g of 85% by mass phosphoric acid was added dropwise thereto, and then 0.825 g of tetraethylammonium chloride was uniformly added. P ₂ 0 ₅ : F- : organic amine: The molar ratio of the ionic liquid was 1: 0.4: 2 : 120 The stirring was continued for 10 minutes, and then the reaction liquid was poured into a reactor in which a ruthenium-cylindrical tubular alumina carrier was placed in advance, and it was noted that the carrier was completely immersed in the reaction liquid, and the ratio of the support to the precursor reaction solution was ( ^(cn^mr ¹ support surface area), the reactor was heated to 150 ° C for 12 hours, then the reactor was cooled to room temperature, the carrier was taken out, ultrasonically washed three times in deionized water, and washed with acetone soaked. After that, the carrier was dried in an oven at 110 ° C. The temperature was raised to 550 ° C at a temperature increase rate of IK/min in a nitrogen atmosphere for 6 hours to remove the organic matter in the pores of the molecular sieve membrane, thereby obtaining an AFI type molecular sieve membrane.

Example 27

65.7 g of 1-butyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 120 ° C. 0.8 g of hydrofluoric acid having a concentration of 40% was uniformly added dropwise, and the mixture was stirred for 2 hours until homogeneous. 0.66 ammonium monohydrogen phosphate was added thereto, and then 0.33 g of tetraethylammonium chloride was uniformly added, P ₂ 0 ₅ : F : organic amine: the molar ratio of the ionic liquid was 1:1.6:0.8:120, and stirring was continued for 10 minutes. Then the reaction solution was poured into a pre-placed δ-round piece. In the reactor of the alumina carrier, it is noted that the carrier needs to be completely immersed in the reaction solution, and the ratio of the support to the precursor reaction solution is 0.2 (cn^mr ¹ support surface area), and the reactor is heated to 140 ° C. After 24 hours, the reactor was then cooled to room temperature, the carrier was removed, ultrasonically washed three times in deionized water, and washed with acetone. The washed carrier was dried in an oven at 110 °C. The organic matter in the pores of the molecular sieve membrane was removed by a temperature increase of 1 K/min to 550 ° C in a nitrogen atmosphere for 6 hours to obtain an AFI type molecular sieve membrane.

Example 28

65.7 g of 1-butyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 100 ° C. 0.168 g of sodium fluoride was uniformly added, stirred for 2 hours until homogeneous, and 0.575 g of phosphoric acid was added thereto. Ammonium hydroxide, then uniformly added 0.33 g of tetraethylammonium chloride, P ₂ 0 ₅ : F : organic amine: ionic liquid molar ratio of 1: 1.6: 0.8: 120, stirring for 10 minutes, then pouring the reaction solution In the reactor in which the δ-square flaky alumina carrier is placed in advance, it is noted that the carrier needs to be completely immersed in the reaction solution, and the ratio of the support to the precursor reaction solution is 0.8 (cn^mr ¹ support surface area), and the reaction is carried out. The temperature was raised to 150 ° C for 12 hours, then the reactor was cooled to room temperature, the carrier was removed, ultrasonically washed three times in deionized water, and washed with acetone. The washed carrier was dried in an oven at 110 °C. The organic matter in the pores of the molecular sieve membrane was removed by a temperature increase of 1 K/min to 550 ° C in a nitrogen atmosphere for 6 hours to obtain an AFI type molecular sieve membrane.

Example 29

65.7 g of 1-butyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 110 ° C. 0.148 g of ammonium fluoride was uniformly added dropwise, stirred for 2 hours until homogeneous, and 0.575 g was added thereto. Phosphoric acid with a concentration of 85%, then uniformly added 0.33 g of tetraethylammonium chloride, stirring was continued for 10 minutes, P ₂ 0 ₅ : F" : organic amine: the molar ratio of ionic liquid was 1:1.6:0.8:120, Then, the reaction liquid is poured into a reactor in which a Θ-cylindrical tubular alumina carrier is placed in advance, and it is noted that the carrier needs to be completely immersed in the reaction liquid, and the ratio of the support to the precursor reaction solution is 0.5 (cn^mr ¹ support) Body surface area), the reactor was heated to 140 ° C for 24 hours, then the reactor was cooled to room temperature, the carrier was removed, ultrasonically washed three times in deionized water, and washed with acetone. The washed carrier was placed at 110 °. Drying in a C oven. The organic matter in the pores of the molecular sieve membrane was removed by heating to a temperature of 4 K/min in an air atmosphere containing 50 mg/L of ozone at a rate of 4 K/min for 6 hours to obtain an AFI type molecular sieve membrane.

Example 30

65.7 g of 1-ethyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, the temperature was raised to 100 ° C, 0.084 g of sodium fluoride and 0.074 g of ammonium fluoride were uniformly added, and stirred for 2 hours until homogeneous. 0.33 g of monoammonium phosphate and 0.29 g of ammonium dihydrogen phosphate were added, and then 0.33 g of tetraethylammonium chloride was uniformly added, P ₂ 0 ₅ : F- : organic amine: the molar ratio of the ionic liquid was 1:1.6: 0.8 : 120, continue to stir for 10 minutes, and then pour the reaction solution into a reactor in which δ-square flaky alumina is pre-positioned. Note that the carrier needs to be completely immersed in the reaction solution, and the ratio of the support to the precursor reaction solution is 0.5 (cn^mr ¹ support surface area), the reactor was heated to 140 ° C for 12 hours, then the reactor was cooled to room temperature, the carrier was taken out, ultrasonically washed three times in deionized water, and washed with acetone. The washed carrier was dried in an oven at 110 °C. In an air atmosphere containing 50 mg/L of ozone, the temperature was raised to 160 ° C at a heating rate of 4 K/min, and held for 4 hours to remove the organic matter in the pores of the molecular sieve membrane, thereby obtaining an AFI type molecular sieve membrane.

Table 4 XRD diffraction peak positions and relative strengths of samples in Examples 23 to 30 of the present invention

It can be seen from the above table that a pure phase AFI type aluminum phosphate molecular sieve membrane can be prepared by using an ionic liquid cation, F- and tetraethylammonium chloride as a structure directing agent within the reaction conditions stated in the method.

Example 31

76.4 g of 1-ethyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 100 ° C. 0.25 g of hydrofluoric acid having a concentration of 40% was uniformly added dropwise, and stirred for 2 hours until homogeneous. 0.575 g of 85% by mass phosphoric acid was added dropwise, and then 0.21 g of N-methylimidazole was uniformly added. P ₂ 0 ₅ : F : organic amine: The molar ratio of ionic liquid was 1: 2 : 1 : 160, continue After stirring for 10 minutes, the reaction liquid was poured into a reactor in which a δ-round flaky alumina carrier was placed in advance, and it was noted that the carrier was completely immersed in the reaction liquid, and the ratio of the support to the precursor reaction solution was 0.5 ( Cn^mr ¹ support surface area), the reactor was heated to 150 ° C for 12 hours, then the reactor was cooled to room temperature, the carrier was taken out, ultrasonically washed three times in deionized water, and washed with acetone. The washed carrier was dried in an oven at 110 °C. The organic matter in the pores of the molecular sieve membrane was removed in the air atmosphere at a temperature increase rate of 1 K/min from room temperature to 550 ° C for 6 hours to obtain a CHA type molecular sieve membrane.

It can be seen from Fig. 13 that the prepared molecular sieve membrane is pure phase and free of heterocrystals; as can be seen from Fig. 14, the prepared molecular sieve membrane is dense, complete and continuous; the thickness is about 20 micrometers; The prepared molecular sieve membrane has good gas permeability.

Example 32

76.4 g of 1-ethyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 120 ° C. 0.125 g of hydrofluoric acid having a concentration of 40% was uniformly added dropwise, and stirred for 2 hours until homogeneous. 0.575 g of 85% by mass of phosphoric acid was added dropwise, and then 0.21 g of N-methylimidazole was uniformly added, and the molar ratio of P ₂ 0 ₅ : F : organic amine: ionic liquid was 1: 1: 1: 160, continue After stirring for 10 minutes, the reaction liquid was poured into a reactor in which a δ-round flaky alumina carrier was placed in advance, and it was noted that the carrier was completely immersed in the reaction liquid, and the ratio of the support to the precursor reaction solution was 0.6 ( Cn^mr ¹ support surface area), the reactor was warmed to 160 ° C for 24 hours, then the reactor was cooled to room temperature, the carrier was removed, ultrasonically washed three times in deionized water, and washed with acetone. The washed carrier was dried in an oven at 110 °C. In the air atmosphere, the temperature was raised to 550 ° C at a heating rate of 1 K / min, and held for 6 h, the organic matter in the pores of the molecular sieve membrane was removed, thereby obtaining a CHA type molecular sieve membrane. Example 33

76.4 g of 1-ethyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 90 ° C. 0.5 g of hydrofluoric acid having a concentration of 40% was uniformly added dropwise, and stirred for 2 hours until homogeneous. 0.23 g of 85% by mass phosphoric acid was added dropwise, and then 0.82 g of N-methylimidazole was uniformly added, and the molar ratio of P ₂ 0 ₅ : F : organic amine: ionic liquid was 1:10:10:400, continue After being stirred for 10 minutes, the reaction solution is poured into a reactor in which a ruthenium-platelet-shaped alumina carrier is placed in advance, and it is noted that the carrier is completely immersed in the reaction solution, and the ratio of the support to the precursor reaction solution is O. cn. ^mr ¹ support surface area), the reactor was warmed to 120 ° C for 480 hours, then the reactor was cooled to room temperature, the support was removed, ultrasonically washed three times in deionized water, and washed with acetone. The washed carrier was dried in an oven at 110 °C. The organic matter in the pores of the molecular sieve membrane was removed in an air atmosphere at a temperature increase rate of IK/min to 550 ° C for 6 hours to obtain a CHA type molecular sieve membrane.

Example 34

76.4 g of 1-ethyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 100 ° C. 0.1 g of hydrofluoric acid having a concentration of 40% was uniformly added dropwise, and stirred for 2 hours until homogeneous. 4.6 g of 85% by mass phosphoric acid was added dropwise, and then 0.164 g of N-methylimidazole was uniformly added, and the molar ratio of P ₂ 0 ₅ : F : organic amine: ionic liquid was 1:0.1:0.1:20, continue After stirring for 10 minutes, the reaction liquid was poured into a reactor in which a γ-cylindrical tubular alumina carrier was placed in advance, and it was noted that the carrier was completely immersed in the reaction liquid, and the ratio of the support to the precursor reaction solution was (^( Cn^mr ¹ support surface area), the reactor was heated to 280 ° C for 0.5 hours, then the reactor was cooled to room temperature, the carrier was taken out, ultrasonically washed three times in deionized water, and washed with acetone soaked. The carrier was dried in an oven at 110 ° C, and raised to 550 ° C in an air atmosphere at a temperature increase rate of IK / min for 6 h to remove organic matter in the pores of the molecular sieve membrane to obtain a CHA type molecular sieve membrane.

Example 35

76.4 g of 1-ethyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 100 ° C, and 0.25 g of 40% hydrofluoric acid was uniformly added dropwise, and stirred for 2 hours until homogeneous. 0.66 g of monoammonium phosphate was added thereto, and then 0.21 g of N-methylimidazole was uniformly added, and the molar ratio of P ₂ 0 ₅ : F : organic amine: ionic liquid was 1:2:1:160, and stirring was continued for 10 minutes. Then, the reaction liquid is poured into a reactor in which a δ-square flaky alumina carrier is placed in advance, and it is noted that the carrier needs to be completely immersed in the reaction liquid, and the ratio of the support to the precursor reaction solution is 0.2 (cn^mr ¹ support) Body surface area), the reactor was warmed to 150 ° C for 12 hours, then the reactor was cooled to room temperature, the carrier was removed, ultrasonically washed three times in deionized water, and the paint was soaked with acetone. The washed carrier was dried in an oven at 110 ° C. The organic matter in the pores of the molecular sieve membrane was removed by raising the temperature to 550 ° C at a temperature increase rate of IK/min in a nitrogen atmosphere for 6 hours to obtain a CHA type molecular sieve membrane.

Example 36

76.4 g of 1-ethyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 90 ° C. 0.21 g of sodium fluoride was uniformly added, stirred for 2 hours until homogeneous, and 0.575 g of phosphoric acid was added thereto. Ammonium hydroxide, then uniformly added 0.21 g of N-methylimidazole, P ₂ 0 ₅ : F : organic amine: the molar ratio of ionic liquid is 1: 2 : 1 : 160, stirring is continued for 10 minutes, then the reaction solution is poured into the In the reactor in which the δ-square flaky alumina carrier is placed, it is noted that the carrier needs to be completely immersed in the reaction solution, and the ratio of the support to the precursor reaction solution is 0.8 (cm^mr ¹ support surface area), and the reactor is The temperature was raised to 150 ° C for 12 hours, then the reactor was cooled to room temperature, the carrier was taken out, ultrasonically washed three times in deionized water, and washed with acetone. Will be washed after The carrier was dried in an oven at 110 °C. The organic matter in the pores of the molecular sieve membrane was removed by raising the temperature to a temperature of 1 K/min to 550 ° C in a nitrogen atmosphere for 6 hours to obtain a CHA type molecular sieve membrane.

Example 37

76.4 g of 1-ethyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 100 ° C. 0.185 g of ammonium fluoride was uniformly added, stirred for 2 hours until homogeneous, and 0.575 g of mass was added thereto. Phosphoric acid with a concentration of 85%, then uniformly added 0.21 g of N-methylimidazole, P ₂ 0 ₅ : F : organic amine: the molar ratio of ionic liquid is 1: 2 : 1 : 160, stirring is continued for 10 minutes, then the reaction is carried out. The liquid is poured into a reactor in which δ-round flake alumina is placed in advance, and it is noted that the carrier needs to be completely immersed in the reaction liquid, and the ratio of the support to the precursor reaction solution is 0.5 (cm^mr ¹ support surface area) The reactor was warmed to 150 ° C for 12 hours, then the reactor was cooled to room temperature, the support was removed, the paint was ultrasonically washed three times in deionized water, and the paint was soaked with acetone. The washed carrier was dried in an oven at 110 ° C. The organic matter in the pores of the molecular sieve membrane was removed in an air atmosphere containing 50 mg/L of ozone at a heating rate of 4 K/min and maintained for 8 hours to obtain a CHA type molecular sieve membrane.

Example 38

82.0 g of 1-propyl-3-methylimidazolium chloride ionic liquid was added to a 100 ml beaker, and the temperature was raised to 90 ° C. 0.0925 g of ammonium fluoride and 0.105 g of sodium fluoride were uniformly added, and stirred for 2 hours until homogeneous. 0.33 g of monoammonium phosphate and 0.29 g of ammonium dihydrogen phosphate were added thereto, and then 0.21 g of N-methylimidazole was uniformly added, and P ₂ 0 ₅ : F" : organic amine: the molar ratio of the ionic liquid was 1:2:1 : 160, continue to stir for 10 minutes, and then pour the reaction solution into a reactor in which δ-cylindrical tubular alumina is pre-placed. Note that the carrier needs to be completely immersed in the reaction solution, and the ratio of the support to the precursor reaction solution is 0.5. (cn^mr ¹ support surface area), the reactor was heated to 150 ° C for 12 hours, then the reactor was cooled to room temperature, the carrier was taken out, ultrasonically washed three times in deionized water, and washed with acetone soaked. The carrier was dried in an oven at 110 ° C. In an air atmosphere containing 50 mg / L of ozone, the temperature was raised to 200 ° C at a heating rate of 4 K / min, and held for 6 h, the organic matter in the pores of the molecular sieve membrane was removed, thereby obtaining CHA. Type molecular sieve membrane.

Table 5 XRD diffraction peak position and relative strength of the samples in Examples 31 to 38 of the present invention

23.23±0.2 weak, weak, strong, weak, strong and weak

23.85±0.2 weak, weak, weak, weak, weak, weak, strong

24.28±0.2 weak, weak, weak, weak, weak, weak

25.06±0.2 strong strong towel, etc. strong strong towel, etc.

26.15±0.2 Strong towels and other strong towels and other strong towels can be seen from the above table. Within the range of reaction conditions stated in the method, ionic liquid cations, F- and N-methylimidazole can be used as structure-directing agents. A pure phase of the CHA type aluminum phosphate molecular sieve membrane is obtained.

Example 39

65.8 g of 1-butyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 100 ° C. 0.10 g of hydrofluoric acid having a concentration of 40% was added dropwise, and stirred for 2 hours until homogeneous. 0.94 g of phosphoric acid with a concentration of 85% was added dropwise, and then 0.75 g of a mass concentration of 25% tetramethylammonium hydroxide was added uniformly, P ₂ 0 ₅ : F" : organic amine: the molar ratio of the ionic liquid was 2:1. : 1 : 150, stirring is continued for 10 minutes, and then the reaction liquid is poured into a reactor in which a δ-round flake alumina carrier is placed in advance, and it is noted that the carrier needs to be completely immersed in the reaction liquid, and the support and precursor reaction solution are The dosage ratio is 0.5 (cn^mr ¹ support surface area), the reactor is heated to 160 ° C for 12 hours, then the reactor is cooled to room temperature, the carrier is taken out, ultrasonically washed three times in deionized water, and soaked in acetone. The washed carrier was dried in an oven at 110 ° C. The temperature was raised to 550 ° C at a heating rate of 1 K / min in an air atmosphere for 6 h to remove the organic matter in the pores of the molecular sieve membrane, thereby obtaining an LTA type. Molecular sieve membrane.

It can be seen from Fig. 16 that the prepared molecular sieve membrane is pure phase and free of heterocrystals; as can be seen from Fig. 17, the prepared molecular sieve membrane is dense, complete and continuous; the thickness is about 20 micrometers; The prepared molecular sieve membrane has good gas permeability.

Example 40

65.8 g of 1-butyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 120 ° C. 0.10 g of a 40% by weight hydrofluoric acid was added dropwise, and the mixture was stirred for 2 hours until homogeneous. 1.88 g of phosphoric acid with a concentration of 85% was added dropwise, and then 0.75 g of a mass concentration of 25% tetramethylammonium hydroxide was added uniformly, P ₂ 0 ₅ : F" : organic amine: the molar ratio of the ionic liquid was 4:1 : 1 : 150, stirring is continued for 10 minutes, and then the reaction liquid is poured into a reactor in which a ruthenium-shaped plate-shaped alumina carrier is placed in advance, and it is noted that the carrier needs to be completely immersed in the reaction liquid, and the support and precursor reaction solution are The dosage ratio is 0.6 (cn^mr ¹ support surface area), the reactor is heated to 170 ° C for 12 hours, then the reactor is cooled to room temperature, the carrier is taken out, ultrasonically washed three times in deionized water, and soaked in acetone. The washed carrier was dried in an oven at 110 ° C. The temperature was raised to 550 ° C at a heating rate of 1 K / min in an air atmosphere for 6 h to remove the organic matter in the pores of the molecular sieve membrane, thereby obtaining an LTA type. Molecular sieve membrane.

Example 41

65.8 g of 1-butyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 100 ° C. 0.20 g of hydrofluoric acid having a mass concentration of 40% was added dropwise, and the mixture was stirred for 2 hours until homogeneous. 1.88 g of phosphoric acid with a concentration of 85% was added dropwise, and then 0.75 g of a mass concentration of 25% tetramethylammonium hydroxide was added uniformly, P ₂ 0 ₅ : F" : organic amine: the molar ratio of the ionic liquid was 4:2 : 1 : 150, stirring is continued for 10 minutes, and then the reaction liquid is poured into a reactor in which a δ-round flake alumina carrier is placed in advance, and it is noted that the carrier needs to be completely immersed in the reaction liquid, and the support and precursor reaction solution are The dosage ratio is 0.4 (cn^mr ¹ support surface area), the reactor will be The temperature was raised to 150 ° C for 24 hours, then the reactor was cooled to room temperature, the carrier was taken out, ultrasonically washed three times in deionized water, and washed with acetone. The washed carrier was dried in an oven at 110 °C. The organic matter in the pores of the molecular sieve membrane was removed by raising the temperature to a temperature of 1 K/min to 550 ° C in an air atmosphere for 6 hours to obtain an LTA type molecular sieve membrane.

Example 42

65.8 g of 1-butyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, and the temperature was raised to 90 ° C. 0.20 g of 40% hydrofluoric acid was added dropwise, and the mixture was stirred for 2 hours until homogeneous. 1.88 g of phosphoric acid with a concentration of 85% was added dropwise, and then 0.75 g of a mass concentration of 25% tetramethylammonium hydroxide was added uniformly, P ₂ 0 ₅ : F" : organic amine: the molar ratio of the ionic liquid was 4:2 : 1 : 150, stirring is continued for 10 minutes, and then the reaction liquid is poured into a reactor in which a γ-cylindrical tubular alumina carrier is placed in advance, and it is noted that the carrier needs to be completely immersed in the reaction liquid, and the support and the precursor reaction solution are The dosage ratio was 0.5 (cm^mr ¹ support surface area), the reactor was heated to 160 ° C for 48 hours, then the reactor was cooled to room temperature, the carrier was taken out, ultrasonically washed three times in deionized water, and washed with acetone. The washed carrier was dried in an oven at 110 ° C. The temperature was raised to 550 ° C at a heating rate of 1 K / min in a nitrogen atmosphere for 6 h to remove the organic matter in the pores of the molecular sieve membrane, thereby obtaining an LTA molecular sieve. membrane.

Example 43

65.8 g of 1-butyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, the temperature was raised to 90 ° C, 0.10 g of 40% by weight hydrofluoric acid was added dropwise, and stirred for 2 hours until homogeneous. 0.47 g of 85% phosphoric acid was added dropwise, and then 0.75 g of a mass concentration of 25% tetramethylammonium hydroxide was added uniformly, P ₂ 0 ₅ : F" : organic amine: ionic liquid in a molar ratio of 1:1 : 1 : 150, stirring is continued for 10 minutes, and then the reaction liquid is poured into a reactor in which a δ-square flaky alumina carrier is placed in advance, and it is noted that the carrier needs to be completely immersed in the reaction liquid, and the support and the precursor reaction solution are The dosage ratio was 0.8 (cn^mr ¹ support surface area), the reactor was heated to 180 ° C for 6 hours, then the reactor was cooled to room temperature, the carrier was taken out, ultrasonically washed three times in deionized water, and washed with acetone. The washed carrier was dried in an oven at 110 ° C. The temperature was raised to 550 ° C at a heating rate of 1 K / min in a nitrogen atmosphere for 6 h to remove the organic matter in the pores of the molecular sieve membrane, thereby obtaining an LTA molecular sieve. membrane.

Example 44

65.8 g of 1-butyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, the temperature was raised to 110 ° C, 0.10 g of 40% hydrofluoric acid was added dropwise, and stirred for 2 hours until homogeneous. 0.47 g of 85% by weight of phosphoric acid was added dropwise, and then 1.50 g of a mass concentration of 25% tetramethylammonium hydroxide was added uniformly, P ₂ 0 ₅ : F" : organic amine: ionic liquid in a molar ratio of 1:1 : 2 : 150, continue to stir for 10 minutes, then pour the reaction solution into a reactor in which a δ-round flaky alumina carrier is placed in advance. Note that the carrier needs to be completely immersed in the reaction solution, and the support and precursor reaction solution The dosage ratio was 0.4 (cn^mr ¹ support surface area), the reactor was heated to 130 ° C for 480 hours, then the reactor was cooled to room temperature, the carrier was taken out, ultrasonically washed three times in deionized water, and soaked in acetone. The washed carrier was dried in an oven at 110 ° C. The temperature was raised to 550 ° C at a heating rate of 1 K / min in a nitrogen atmosphere for 6 h to remove the organic matter in the pores of the molecular sieve membrane, thereby obtaining an LTA type. Molecular sieve membrane.

Example 45

65.8 g of 1-butyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, the temperature was raised to 110 ° C, 0.10 g of 40% hydrofluoric acid was added dropwise, and stirred for 2 hours until homogeneous. Which added 0.47 g of mass Phosphoric acid with a concentration of 85%, then uniformly added 1.50 g of 25% tetramethylammonium hydroxide, P ₂ 0 ₅ : F" : organic amine: ionic liquid in a molar ratio of 1: 1: 2: 150, continue After stirring for 10 minutes, the reaction solution was poured into a reactor in which a δ-round flaky alumina carrier was placed in advance, and it was noted that the carrier was completely immersed in the reaction solution, and the ratio of the support to the precursor reaction solution was 0.4 ( Cn^mr ¹ support surface area), the reactor was heated to 140 ° C, held for 168 hours, then the reactor was cooled to room temperature, the carrier was taken out, ultrasonically washed three times in deionized water, and washed with acetone soaked. The carrier was dried in an oven at 110 ° C. In an air atmosphere containing 50 mg / L of ozone, the temperature was raised to 150 ° C at a heating rate of 4 K / min, and held for 6 h, the organic matter in the pores of the molecular sieve membrane was removed, thereby obtaining an LTA type. Molecular sieve membrane.

Example 46

65.8 g of 1-butyl-3-methylimidazolium iodide ionic liquid was added to a 100 ml beaker, the temperature was raised to 110 ° C, 0.10 g of 40% hydrofluoric acid was added dropwise, and stirred for 2 hours until homogeneous. 0.47 g of 85% by mass of phosphoric acid was added dropwise, and then 0.075 g of a mass concentration of 25% tetramethylammonium hydroxide was added uniformly, P ₂ 0 ₅ : F" : organic amine: ionic liquid in a molar ratio of 1:1 : 0.1 : 150, continue to stir for 10 minutes, then pour the reaction solution into a reactor in which a δ-round flaky alumina carrier is placed in advance. Note that the carrier needs to be completely immersed in the reaction solution, and the support and precursor reaction solution The dosage ratio was 0.8 (cm^mr ¹ support surface area), the reactor was heated to 130 ° C for 480 hours, then the reactor was cooled to room temperature, the carrier was taken out, ultrasonically washed three times in deionized water, and soaked in acetone. Washing. The washed carrier was dried in an oven at 110 ° C. It was raised to 160 ° C at a heating rate of 4 K / min in an air atmosphere containing 50 mg / L of ozone, and kept for 4 h to remove the pores in the pores of the molecular sieve membrane. Organic matter, thereby obtaining LTA type Sieving membranes.

Table 6 XRD diffraction peak position and relative strength of the samples in Examples 39 to 46 of the present invention

It can be seen from the above table that a pure phase LTA type aluminum phosphate molecular sieve membrane can be prepared by using an ionic liquid cation, F- and tetramethylammonium hydroxide as a structure directing agent within the range of reaction conditions claimed in the method.

Claims

Claim

A method for preparing an aluminum phosphate molecular sieve membrane supported by a porous alumina carrier, characterized in that: using an ionic liquid as a reaction medium, with a support of a structure directing agent, a porous alumina carrier as a support, on the surface of the support Synthesizing a microporous aluminum phosphate molecular sieve membrane; wherein the structure directing agent is one or more of an ionic liquid cation, F, and an organic amine;

The specific operation process is as follows.

1) Preparation of precursor reaction solution: The ionic liquid is mixed with the phosphorus-containing raw material, the fluorine-containing raw material and the organic amine, and stirred to form a precursor reaction solution, and the reaction solution is P ₂ 0 _5: F: organic amine: molar of the ionic liquid The ratio is 1: 0~10: 0~10: 20~ shed;

3) After the crystallization is completed, the porous alumina carrier is taken out, and the organic template is removed to obtain an aluminum phosphate molecular sieve membrane.

2. The preparation method according to claim 1, wherein the crystal structure and orientation of the obtained zeolite membrane can be changed by adjusting the composition of the structure directing agent:

2Θ indicates the position of the diffraction peak, 2θ/°: 6.80±0.2; 9.77±0.2; 13.63±0.2; 18.35±0.2; 20.52±0.2; 21.27±0.2; 22.33±0.2; 22.95±0.2; 23.45±0.2; 25.40±0.2 ; 25.81±0.2; 28.16±0.2; 29.56±0.2;

2) When the structure directing agent is an ionic liquid cation and F, the molecular sieve crystal of the obtained molecular sieve membrane has an AEL structure confirmed by the International Zeolite Association, and the molecular sieve crystal constituting the molecular sieve membrane has a one-dimensional ten-membered ring straight pore structure, and the pore size is 0.65 nm x 0.40 nm, the X-ray diffraction spectrum of which has at least the following diffraction peaks:

The orientation of the AEL zeolite membrane can be adjusted by adjusting the concentration of F in the precursor reaction solution;

3) When the structure directing agent is ionic liquid cation, F- and tetraethylammonium chloride, the molecular sieve crystal of the obtained molecular sieve membrane has the AFI structure confirmed by the International Zeolite Association, and the AFI structural aluminum phosphate molecular sieve has a one-dimensional twelve-membered ring channel. The pore size is 0.73 _n mx0.73 nm, and the X-ray diffraction spectrum thereof has at least the following diffraction peaks: 2Θ indicates the position of the diffraction peak, 2θ/°: 7.80±0.2; 13.27±0.2; 15.28±0.2; 20.15± 0.2; 21.36±0.2; 22.79±0.2; 25.12±0.2; 26.36±0.2; 29.42±0.2;

4) When the structure directing agent is an ionic liquid cation, F and Ν-methylimidazole, the molecular sieve crystal of the obtained molecular sieve membrane has a CHA structure confirmed by the International Zeolite Association, and the molecular sieve crystal structure constituting the molecular sieve membrane comprises a double six-membered ring connected The chabazite cage has an eight-membered ring window and a four-ring structure connected adjacent to each other, having a pore size of 0.38 nm X 0.38 nm, and an X-ray diffraction spectrum having at least the following diffraction peaks:

2Θ indicates the position of the 3⁄4ί peak, 2θ/°: 9.40±0.2; 12.05 ± 0.2; 13.81 ± 0.2; 15.20 ± 0.2; 15.53 ± 0.2; 17.87 ± 0.2; 18.45 ± 0.2; 19.35 ± 0.2; 19.75 ± 0.2; 21.31 ± 0.2; 21.74 + 0.2; 22.50 ± 0.2; 23.23 ± 0.2; 23.85 ± 0.2; 24.28 ± 0.2; 25.06 ± 0.2; 26.15 ± 0.2; 5) when the structure directing agent is ionic liquid cation, F and tetramethylammonium hydroxide Molecular sieve membrane The molecular sieve crystal has the LTA structure confirmed by the International Zeolite Association. The molecular sieve crystal structure constituting the molecular sieve membrane has a three-dimensional cross-cell structure, and has a super-cage structure with an eight-membered ring window formed by a SOD cage through a double four-membered ring link, and the aperture size is 0.41. nmX 0.41nm, its X-ray diffraction spectrum has at least the following diffraction peaks: 2 Θ value indicates 3⁄4ί peak position, 2 θ /°: 7.28 ± 0.2; 10.34 ± 0.2; 12.49 ± 0.2; 12.69 ± 0.2; ± 0.2; 16.47 ± 0.2; 18.06 ± 0.2; 20.91 ± 0.2; 21.88 ± 0.2; 22.22 ± 0.2; 23.44 ± 0.2; 24.61 ± 0.2; 26.81 ± 0.2; 27.84 ± 0.2.

3. The preparation method according to claim 1, wherein the reaction medium is an ionic liquid, and the cation of the ionic liquid is: an alkyl quaternary ammonium salt [NR4] ⁺ , an alkyl quaternary phosphonium ion [PR4] ⁺ , One of an alkyl-substituted imidazolium ion [Rim] ⁺ , an alkyl-substituted pyridinium ion [Rpy] ⁺ , R is a C1 - C16 alkyl group; wherein the anion of the ionic liquid is: Br -, Cl -, hydrazine, One of BF ₄ -, PF ₆ -, P0 ₄ ³ -, N0 ₃ -, S0 ₄ ² -.

The method according to claim 1, wherein the phosphorus-containing raw material is one or more of phosphoric acid, ammonium phosphate, monoammonium phosphate or ammonium dihydrogen phosphate;

The fluorine-containing raw material is one or more of hydrofluoric acid, ammonium fluoride or sodium fluoride.

5. The preparation method according to claim 1, wherein: the porous alumina carrier is used as a support; and the alumina crystal phase of the porous alumina carrier may be Y-alumina, δ-alumina or yttrium-alumina. One of the support and precursor reaction solutions is calculated from the ratio of the surface area of the support in contact with the solution to the volume of the precursor reaction solution, which is the surface area of the support of 0.2 to 0.8 cm ² per ml of solution.

The preparation method according to claim 1, wherein the molar ratio of P ₂ 0 _{5 :} F: organic amine: ionic liquid in the precursor reaction solution is 1: 0-2: 0-2: 40~160 .

The method according to claim 1, wherein the crystallization temperature is 120 to 280 ° C and the crystallization time is 0.5 to 480 h.

The method according to claim 1, wherein the precursor reaction solution has a water content of 0 to 10% by weight based on the weight of the precursor reaction solution.

The preparation method according to claim 8, wherein the water in the precursor reaction solution is carried in by a raw material or may be additionally added.